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US6242561B1 - Substituted polythiophenes, processes for their preparation their use - Google Patents

Substituted polythiophenes, processes for their preparation their use Download PDF

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US6242561B1
US6242561B1 US09/142,201 US14220199A US6242561B1 US 6242561 B1 US6242561 B1 US 6242561B1 US 14220199 A US14220199 A US 14220199A US 6242561 B1 US6242561 B1 US 6242561B1
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group
branched
linear
chain
thiophene
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Helmut Möhwald
Vladimir Belov
Wolfgang Schrof
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HC Starck GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a polythiophene, comprising structural units of the general formulae (I) and (II)
  • X and Y independently of one another can be identical or different and are a linear or branched-chain C 1 - to C 22 -alkyl group; a linear or branched-chain C 1 - to C 22 -alkoxy group; a linear or branched-chain C 1 - to C 22 -alkoxyalkyl group; a linear or branched-chain C 1 - to C 22 -acyl group; a linear or branched-chain C 1 - to C 22 -thioacyl group; a linear or branched-chain C 1 - to C 22 -acyloxy group; a linear or branched-chain C 1 - to C 22 -thioacyloxy group; a C 5 - to C 8 -cycloalkyl group, a C 6 - to C 18 -aryl group or a C 5 - to C 8 -heterocyclic group, which in each case can in turn be substituted by one or more linear or branched-chain
  • this ring system can in turn be substituted on the carbon atom(s), the nitrogen atom(s) or the phosphorus atom(s) in each case by a group Z, where each Z independently of one another is a group as defined above for X and Y, or
  • A is carbon (C), nitrogen (N), phosphorus (P) or mixtures of two or more of these atoms,
  • each of these As can either carry a hydrogen atom or can in turn be substituted as defined above for X and Y, obtainable by the Stille reaction, wherein 2,5-dihalothiophene or 2,5-ditriflatethiophene and thiophene derivatives which are bis(trialkyltin)-substituted on the carbon atoms adjacent to the sulfur, which correspond to the structural unit (II) defined above, or 2,5 bis(trialkyltin)thiophene and thiophene derivatives which are bis(halo)- or bis(triflate)-substituted on the carbon atoms adjacent to the sulfur, which correspond to the structural unit (II) defined above, are reacted with one another in suitable solvents in the presence of suitable Pd(0) or Pd(II) complexes or salts thereof as catalyst, or the Suzuki reaction, wherein 2,5-dihalo- or 2,5-triflate-substituted thi
  • Polythiophenes are an important class of conjugated polymers having high electrical conductivity and nonlinear optical properties and can be used as materials for semiconductors (see, inter alia, EP-B-0 332 704 and P. N. Prasad, D. J. Williams “Introduction to NLO effects in molecules and polymers”, John Wiley and Sons, Inc. (1991)).
  • the polythiophenes furthermore have electrochromic and antistatic properties (see N. Arsalani and K. E. Geckeler “Conducting isopolymers: preparation, properties, and applications”, J. Prakt. Chem. 337 (1995, pp. 1-11)).
  • the J 60 120 722 relates to linear copolymers comprising 5-membered heterocyclic compounds having functional groups being selected among halogen, hydroxy, amino or carbohydrate groups, as defined therein. These copolymers are produced by anodic oxidation.
  • the JP 63 344 578 relates to the preparation of an electrically conductive polymer being constituted of 3,4-substituted heterocyclic 5-membered ring compounds, by means of a polymerization in the presence of an oxidizing agent, such as iron chloride, in an organic solvent.
  • an oxidizing agent such as iron chloride
  • ⁇ -Stannylthiophen of formula (n-butyl) 3 Sn(C 4 H 2 S) 3 —Sn(n-butyl) 3 is disclosed in J.Org.Chem. 1995, 60, pp. 6813-6819.
  • Soluble poly(2,3-dihexylthieno[3,4-b]pyrazines) were prepared by M. Pomerantz et al. by iron chloride/oxygen polymerization of the corresponding monomers (see M. M. Pomerantz “New processable low band-gap, conjugated polyheterocycles”, Synthetic Metals, 55-57, pp. 960-965 (1993), and J. Chem. Soc. Commun. 1992, pp. 1672-73). By means of this process, only doped substances can be prepared. Even after treatment with aqueous ammonia or hydrazine, an EPR signal and line widening in the NMR spectra were observed, which points to the presence of paramagnetic species.
  • a further, general starting point for the preparation of oligo- or polythiophenes includes the catalytic coupling of organometallic reagents (usually Grignard reagents) (see Kricheldorf, loc. sit.).
  • thiophenes with functional groups such as, for example, nitro, carbonyl, imino, amido, nitrile, pyridine and pyrazine groups, cannot be employed in this process.
  • a relatively new process for the preparation of new C—C linkages is the Stille reaction.
  • an organic electrophile is reacted with an organotin reagent in the presence of a suitable solvent and of a Pd(0) or Pd(II) complex
  • Pd(0) or Pd(II) complex see J. K. Stille “The palladium-catalyzed cross-coupling reactions of organotin reagents with organic electrophiles”, Angew. Chem. Int. Ed. Engl. 25, pp. 508-542 (1986)).
  • This reaction has already been successfully carried out for the preparation of poly(2,5-thieno-1,4-phenylenes) according to the following scheme (see Z. Bao et al., J. Am. Chem. Soc., 117, 12426-12435 (1995)).
  • the doping leads to new electronic states, which are desirable for certain applications, such as, for example, relatively high electrical conductivity, but are undesirable for other applications, such as, for example, the preparation of thin films having good optical quality.
  • the properties of doped materials often change as a function of time. Furthermore, the reproducibility of their properties is in general also lower compared with the properties of undoped substances.
  • the object of the present invention is thus the provision of novel polythiophenes which have more than one structural unit, which units are different from one another, and can be used advantageously in various industrial areas as outlined above.
  • the structural unit (I) present in the polythiophenes according to the invention is derived from thiophene.
  • X and Y are identical. If X and Y are each the group NHR 1 , the two radicals R 1 are preferably also identical. Under the alkyl, alkoxy, alkoxyalkyl, acyl and thioacyl groups with 1 to 22 C-atoms, as listed above, those having 1 to 20 carbon atoms are preferred, those having 6 to 20 carbon atoms are more preferred, those having 10 to 16 carbon atoms particularly preferred.
  • X and Y substituents are the acyl groups, thioacyl groups and NHR 1 defined above.
  • thioacyl group designates a group of the general formula —C(S)-R, where R is alkyl.
  • heterocyclic group designates alicyclic saturated, alicyclic unsaturated and aromatic heterocyclic groups.
  • X and Y together with the atoms to which they are bonded, can form a carbon-containing ring system which beside carbon contains nitrogen (N), oxygen (O), sulfur (S) or phosphorus (P) heteroatoms or mixtures of two or more of these heteroatoms.
  • X and Y in this case form a divalent radical which has two to eight atoms, additionally preferably three to six atoms, and, together with the two atoms to which it is bonded, forms a ring system having four to ten or five to eight atoms.
  • the number of heteroatoms defined above possibly present in this ring system is preferably up to three, additionally preferably up to two.
  • nitrogen (N) is preferred.
  • the ring system described above is a system having at least one, additionally preferably two or more double bonds.
  • the double bonds of the above ring system are conjugated with the double bonds of the thiophene fragment to which the ring system is bonded, and, if appropriate, to the double bonds of further radicals of the formulae (III) to (VI), as defined in claim 1 , bonded to the ring system described above.
  • This ring system can in turn be substituted on the carbon, nitrogen or phosphorus atoms, in each case by a group Z, where each Z independently of one another is a group as defined above for X and Y, and here too the substituents preferably indicated for X and Y are in turn to be regarded as preferred.
  • Two adjacent groups Z can moreover together form a radical which is selected from among the radicals of the general formulae (III) to (IV) mentioned at the outset, the symbol “A” being carbon (C), nitrogen (N), phosphorus (P) or mixtures of two or more or these atoms, it being possible, if A is carbon, for this either to carry a hydrogen atom or in turn, as defined above for X and Y, to be substituted.
  • Preferred rings resulting in this case which may be mentioned is the cyclobutene ring.
  • a preferred group of the polythiophenes according to the invention are those having structural units of the general formulae (VII) and/or (VIII)
  • X and Y are as defined above and n, m and k independently of one another are an integer from 1 to 10, preferably an integer from 1 to 6, and 1 is an integer from 1 to 3000, preferably 1 to 1000, in particular 1 to 100.
  • the alternating sequence of a substituted thiophene unit and an unsubstituted thiophene unit is preferred.
  • polythiophenes are those in which the structural unit (II) is selected from the group consisting of the radicals of the following general formulae
  • R 2 is CH 2 R 1 or R 2 is CHR 1 2
  • R 1 is H or as defined in claim 1 , under the proviso that radicals of the general formula (IIg) wherein R 1 being hydrogen are excluded.
  • the proportions of the structural units (I) and (II) defined above in the polythiophenes according to the invention is from approximately 1 to approximately 99 mol % (I) and from approximately 99 to approximately 1 mol % (II), preferably from approximately 30 to approximately 70 mol % (I) and from approximately 70 to approximately 30 mol % (II) and in particular from approximately 50 mol % (I) to approximately 50 mol % (II), the proportions of these two structural units in each case adding up to 100 mol %.
  • the sequence of the two structural units (I) and (II) is alternating.
  • the weight average molecular weight (M w ) of the polythiophenes prepared according to the invention is in general from approximately 1000 to approximately 500,000, preferably from approximately 10,000 to approximately 250,000, and in particular from approximately 30,000 to approximately 80,000.
  • the inhomogeneity of the molecular weight distribution ie. the quotient of the weight average molecular weight and the number average molecular weight (M w /M n ), is from approximately 2 to approximately 4, preferably from approximately 2 to approximately 3, and in particular from approximately 2 to approximately 2.5.
  • the processes for preparing the polythiophenes according to the invention are the reaction according to Stille, which has already been mentioned in the introduction, and the reaction according to Suzuki (see A. Suzuki et al., “Stereoselective synthesis of arylated (E)-alkenes by the reaction of alk-1-enylboranes with aryl halides in the presence of palladium catalyst”, J.C.S. Chem. Comm., 1979, pp. 866-867) which will be explained in greater detail in the following.
  • Preferred boranes employed in this reaction are thiophene-2,5-diboric acid and esters thereof. With respect to further details of this reaction, reference is made to the literature source referred to above.
  • the particularly preferred process for preparing the polythiophenes according to the invention is the Stille reaction already mentioned at the outset.
  • 2,5-dihalothiophene or 2,5-ditriflatethiophene and thiophene derivatives which are bis(trialkyltin)-substituted on the carbon atoms adjacent to the sulfur, which correspond to the structural unit (II) defmed above, or 2,5 bis(trialkyltin)thiophene and thiophene derivatives which are bis(halo)- or bis(triflate)-substituted on the carbon atoms adjacent to the sulfur, which correspond to the structural unit (II) defmed in claim 1 , are reacted with one another according to the following scheme in suitable solvents in the presence of suitable Pd(0) or Pd(II) complexes or salts thereof as catalyst.
  • halogen-substituted derivatives are preferably employed. If bis(triflate)-, ie. (CF 3 SO 3 )-substituted starting materials are employed, LiCl, for example, can be added to improve the reactivity.
  • the catalysts employed are Pd(II) or Pd(0) complexes.
  • Preferred catalysts which may be mentioned are, in particular, the following: tris(dibenzylideneacetone)dipalladium (Pd 2 dba 3 ), Pd(Ph 3 P) 2 Cl 2 , “Ph” being C 6 H 5 , and Pd(Ph 3 P) 4 .
  • tris(dibenzylideneacetone)dipalladium Pd 2 dba 3
  • Pd(Ph 3 P) 2 Cl 2 “Ph” being C 6 H 5
  • Pd(Ph 3 P) 4 When using tris(dibenzylideneacetone)dipalladium, various ligands can be added, the catalytically active catalyst PdL 4 being formed in situ by ligand exchange between the weakly coordinated Pd2dba 3 and the ligand(s).
  • the ligands used in this case are PPh 3 , AsPH 3 ,[2-(CH 3 )C 6 H 4 ] 3 P, P(OPh) 3 and (2-furyl) 3 P, “furyl” being a 2-furyl group.
  • the amount of the catalyst employed is from approximately 2 to approximately 10 mol %, preferably about 2 to about 5 mol %, based on the amount of bis(trialkyltin)-substituted starting material employed.
  • DMF dimethyl methacrylate
  • NMP cyclic ethers
  • cyclic ethers such as, for example, THF and dioxane
  • the reaction is in general carried out at temperatures between room temperature and the boiling point of the solvent, temperatures from approximately 50° C. to approximately 100° C. being preferred.
  • the reaction time varies between 1 day and 1 month, preferably 1 day to 1 week.
  • the Suzuki reaction also has the abovementioned advantages compared with the conventional methods, in the context of the present invention the Stille reaction is particularly preferred since, in contrast to the Suzuki reaction, it needs no additional base.
  • the present invention furthermore provides compounds of the general formulae (IXa) to (IXc)
  • “Sub” is hydrogen (H), bromine (Br), chlorine (Cl), iodine (I), triflate (CF3SO 3 ) or trialkyltin, and R 1 is as defmed above, and R 2 is CH 2 R 1 or CHR 1 2 , under the proviso that, if in compound IXa both “Sub” are identical and respectively hydrogen, R 1 may not have the following meaning:
  • R 1 are identical and represent hydrogen, methyl or C 6 H 13
  • R 1 are different from each other and represent methyl and hydrogen.
  • this class of monomer can in general be prepared according to conventional processes for the preparation of such compounds, the general process for the preparation of the monomers according to the invention illustrated in the examples is preferably used.
  • Thin films of the polythiophenes according to the invention can be prepared by pouring carefully filtered or centrifuged solutions in chloroform or trichloroethylene onto a glass substrate. By means of this process, homogeneous films having a thickness of up to 300 nm can be obtained. The optical quality of the films is high and exhibits no noticeable scattering of the light.
  • the positions of the maxima in the long-wave region of the solutions or films of all copolymers which contain thieno[3,4-b]pyrazine units IIb to IIe is determined by their relative proportion and is in the range from approximately 400 to approximately 1000, particularly approximately 410 to approximately 900 nm.
  • polythiophenes described herein can be used either undoped or doped for the antistatic finishing of substances which do not or only poorly conduct electrical current, as electrically conductive films, as semiconductor films, as additive for active electrodes, for LEDs, as organic transistors and capacitors.
  • these copolymers are processed in the customary manner and, if appropriate, mixed with known additives and formulating substances which are necessary for the particular application or processed according to known processes.
  • the present invention additionally provides a process for the antistatic finishing of substances which do not or only poorly conduct electrical current by applying a layer comprising an electrically conductive organic polymers to the surface of the substrates, which comprises producing on the surface of the substrates by polymerization a layer of at least one polythiophene which contains the structural units of the general formulae (I) and (II) defined above.
  • the above-mentioned layer may be also exclusively composed of the above defined conductive oganic polymer.
  • the present invention furthermore provides an electrically conductive material which contains at least one polythiophene according to the present invention.
  • the components 1 and 3 were reacted in THF in the presence of (Ph 3 P) 4 Pd or (Ph 3 P) 2 PdCl 2 , which was used in a catalytic amount of from 2 to 5 mol %, based on the component 1 shown in the scheme below. With the dibromide 1 shown below, the reaction began at room temperature.
  • m and k are each an integer of 1 to 10 and 1 is an integer of 1 to 3000, R is alkyl, ⁇ max is the wavelength of the maximum absorption in the visible range.
  • Short oligomers 7, 8 and 9 were separated from the reaction mixture and obtained as pure compounds after separation by means of a silica gel column. A fraction of “longer oligomers” which was obtained after separation was investigated by mass spectroscopy using matrix-asssted laser-
  • MALDI mass-desorption ionization
  • the values possible for m are 1,2 and 3. If m is 1, the set of k values can be 1,2,2 or 1,1,3, rearrangements being possible within the first set which then lead to a set 2,1,2 or 2,2,1, which correspond to three isomeric oligomers.
  • polymers are obtained whose elemental analysis approximately has a 1:1 ratio of the two monomers.
  • the weight average molecular weight (M w ) of the polymers of the general formula 4 obtained starting from 1 and 3 which are obtained in the context of this reaction is from approximately 20,000 to approximately 100,000, preferably approximately 50,000, in each case measured by GPC using polystyrene as a standard.
  • the polydispersity (M w /M n ) is from approximately 2.0 to approximately 3.0, preferably from approximately 2.0 to 2.5.
  • copolythiophenes having a weight average molecular weight from approximately 30,000 to approximately 60,000, preferably to approximately 50,000, and a polydispersity of from approximately 2.0 to approximately 3.0 are obtained.
  • polythiophenes of the general formulae 4, 5 and 6 with alkyl (or alkoxyalkyl) substituents having 10 to 22 carbon atoms are soluble in organic solvents, such as, for example, chloroform and THF.
  • a further, very interesting modification of the thieno[3,4-b]pyrazine fragment includes the extension of the conjugation within the pyrazine component to be polymerized.
  • This additional conjugated system can be heterocyclic or nonheterocyclic. In the latter case, it can be constructed of one, two or more C ⁇ C double bonds with formation of 4-, 6-, etc.-membered rings.
  • the 4-membered ring system of cyclobuta[b]thieno[3,4-e]pyrazine 10 is of particular interest, as it represents a novel unusual polythiophene type having a special electron density distribution and thus novel physical properties.
  • 5,7-Dibromothieno[3,4-b]pyrazines of the general formula 11, which are interesting monomers for the synthesis of undoped or doped poly- and oligothiophenes of the general formulae 4 and 6, as defined above, are preferably obtained as follows:
  • Preferred embodiments of the above monomer 11 are the monomers of the general formulae 14 and 17 described below.
  • 2-alkyl(aryl)-3-alkoxy-5,7-dibromothieno[3,4-e]pyrazines may be synthesized as follows:
  • compound 10 (3-alkyl-5,7-dibromo-1,2-dihydro-2-oxothieno[3,4-e]pyrazine) is similar to the compound as obtained by starting from 3,4-diaminothiophene and ethylpyruvate by F. Outurquin, P. Lerouge and C. Palmier (Bull., Soc. Chem. Fr., 1086, 2, pp. 267-275). However, the product described therein comprised no bromine atoms and their further chemical conversion is different from the reactions carried out herein.
  • the 5,6-dialkoxy-1,3-dibromocyclobuta(b)thieno[3,4-e]pyrazines of the general formula 17 can be obtained as follows:
  • the 5,7-dibromo- or 5,7-diiodo-1,2,3,4-tetrahydro-2,3-dioxothieno[3,4-b] pyrazines 13 can be obtained starting from the known compound 12 (see F.Outurquin et al., Bull. Chem. Soc. France 1983, 5-6, 11-153-II-154) in a yield of 60 to 90% as a yellowish-brown to dark brown powder. It has an extremely low solubility in virtually all solvents, but its quality can be checked by microanalysis for the Br or I content (see F. Outurquin et al., loc. cit.)
  • the monomers 14 and 17 can be prepared starting from the amides 13 or the compounds 16 by O,O′-alkylation with the corresponding iodides (RCH 2 I) under similar conditions indicated in G. C. Hopkins et al., J. Org. Chem. 32, p. 4040 (1967).
  • O,O′-alkylation predominates compared with an N,N′-alkylation if the reaction is carried out in an aprotic nonpolar solvent, preferably in a hydrocarbon. Toluene is particularly preferably used, as it permits a reaction at higher temperatures.
  • the starting compound 15 is obtained in a simple manner and high yield starting from 3,4diaminothiophene and commercially available 1,2-diethoxy-2,3-dioxocyclobutene according to the process described by A. H. Schmidt et al. in Synthesis, p. 869 (1978). The bromination and O,O′-dialkylation are then carried out in the same manner as described above and the monomer 17 is obtained.
  • the isolation and purification of the monomers 14 and 17 is carried out by chromatography on a silica gel column and subsequent recrystallization.
  • the compounds obtained are stable in air at room temperature. Their thermal stability is also adequate for the subsequent reactions, and no degradation in solution was observed at temperatures up to 100-120° C. under a protective gas atmosphere over several hours.
  • a further interesting class of monomer are the N,N-substituted 3,4-diamino-2,5-diiodothiophenes of the general formula 18. These can be obtained as follows:
  • 11-Docosyne was oxidized according to the general process shown above (D. G. Lee et al., Synthesis, 1978, pp. 462-463). 11-Docosyne (prepared according to the process described by T. M. Fyles in J. Org. Chem. 1984, pp. 753-761) (15.3 g, 0.05 mol) and Adogen® 464 (5.7 g, obtainable from ALDRICH) were dissolved in a mixture of 360 ml of dichloromethane and 18 ml of glacial acetic acid. Potassium permanganate (21.6 g, 0.136 mol) was finely powdered and added to the solution which was kept at reflux and vigorously stirred. This mixture was stirred under reflux for four hours.
  • This substance has a limited stability and was employed in the other reactions without further purification.
  • This compound was obtained in 39% yield (of theory) in a similar manner starting from dodecane-6,7-dione and 3,4-diamino-2,5-dibromothiophene dihydrobromide. It has a melting point of 103.0-103.5° C. (decomposition) (from methanol).
  • This compound was prepared in a yield of 70% of theory starting from 3,4-diaminothiophene and palmitoyl chloride (boiling point 141° C. at 1.4 mbar) in a similar manner to above.
  • the melting point was 107-109° C. (from toluene-hexane).
  • This compound was prepared in a similar manner to above in a yield of 83% of theory. Its melting point was 201-203° C. (decomposition) (toluene-ethanol).
  • 2,2′:5′2′′-terthiophene (2.48 g, 10 mmol) was dissolved in dry THF.
  • the solution was deoxygenated by passing in a gentle stream of nitrogen, cooled to ⁇ 50° C., and 8.0 ml of 2.5 M n-BuLi in hexane (20 mmol) were added dropwise with stirring. The cooling bath was removed, and the reaction mixture was stirred at room temperature for a further 4 hours.
  • Trimethyltin chloride (4.0 g 20 mmol) dissolved in 15 ml of THF was then added and the mixture was stirred overnight.
  • the THF was evaporated, the residue was dissolved in ether, and the ether solution was washed with water and alkali solution and then dried over MgSO 4 .
  • the solvent was evaporated, and the solid was taken up in hexane and filtered by means of Celite®.
  • the hexane was evaporated, and a green oil which crystallized to give a green solid was obtained. This was washed with methanol and dried over CaCl 2 in a desiccator. The yield was 2.8 g (50% of theory).
  • the melting point was 107-110° C.
  • the starting material 12 was obtained according to the process described by F. Outurquin in Bull. Chem. Soc. France, 1983, II-153-159 (process A) and crystallized from water with addition of active carbon and the evaporation of the mother liquor to a small volume.
  • the dioxane-bromine complex (1:1, 1.75 g, 7.1 mmol) was added under nitrogen in small portions to the stirred suspension of the compound 12 (0.49 g, 2.9 mmol) in 20 ml of dry THF at ⁇ 10° C. After addition was complete, the cooling bath was removed, and the reaction mixture was allowed to warm to room temperature and was stirred for 6-10 hours. A brown precipitate was filtered off, washed with ether and dried. 0.64 g (67% of theory) of a crude product of the compound 13 was obtained.
  • the starting material 13 (0.59 g, 1.8 mmol), silver carbonate (1.10 g, 4.9 mmol) and hexadecyl iodide (7.0 g, 20 mmol) were suspended in toluene (70 ml) and the mixture was kept for 30 minutes under nitrogen in an ultrasonic bath at room temperature. During the course of this, evolution of gas was observed. The reaction mixture was then stirred for 6-8 hours at 100° C. under nitrogen and kept in an ultrasonic bath (30 min, room temperature, nitrogen atmosphere). This process was repeated 6 to 8 times, the entry of bright daylight being excluded.
  • Triethylamine (0.48 g, 4.7 mmol) was added dropwise to a stirred suspension of 3,4-diamino-2,5-dibromothienophene dihydrobromide (2.06 g, 4.7 mmol) in 30 ml water-free ethanol at 0 to 5° C. Stirring was continued at the same temperature for 30 min. Subsequently ethylpyruvate (0.58 g, 5 mmol) was added dropwise at the same temperature. The reaction mixture was allowed to warm to room temperature and was stirred for 16 h. Subsequently, it was poured into an excess of ice water, the precipitate was collected, washed with water and dried in vacuum at room temperature.
  • the substance started to degrade at temperatures of above 200° C. without melting.
  • Triethylamine (0.20 g, 2 mmol) was added to a stirred suspension of 3,4-diamino-2,5-dibromothiophene dihydrobromide (1.15 g, 2.66 mmol) in 20 ml water-free ethanol at 0 to 5° C. Stirring was continued at the same temperature for 30 min, and subsequently ethyl-2-oxobutanoic acid (0.27 g, 2.66 mmol) which was dissolved in 5 ml wash-free ethanol, was added dropwise. The reaction mixture was allowed to warm up to room temperature and stirring was continued for 16 h.
  • Starting material 10 was used in amounts of several mmol. It is, however, also possible to carry out reactions in a larger range. To this starting material silver carbonate in equivalent molecular amounts and toluene (50-100 ml) were added and the reaction mixture was ultrasonicated at room temperature under nitrogen for 30 min.
  • alkyl iodide (50-Subsequently alkyl iodide (10-fold excess of primary or secondary iodide) added in one batch and stirring was continued for further 10 to 20h at 60-70° C., and every 3 to 4 h it was ultrasonicated for 5 min. Subsequently, the mixture was filtered through Celite, the filter cake was washed with hexane, the filtrate was evaporated under vacuum and the product of the O-alkylation was isolated by chromatography over silica.
  • the starting material 16 (0.20g, 0.57 mmol), silver carbonate (0.32 g, 1.20 mmol) and dodecyl iodide (3.0 g, 10 mmol) were stirred at room temperature for 3 weeks in toluene.
  • the mixture was filtered through Celite®, the filter cake was washed with ether, and the combined solutions were evaporated, the residue was taken up in hexane and the mixture was separated on a silica gel column.
  • the excess of dodecyl iodide was removed by means of hexane.
  • the desired product was eluted using a hexane-ether mixture (19:1 ⁇ 9:1).
  • the yield was 0.094 g (24% of theory) of a yellowish-green oil which crystallized at room temperature.
  • the melting point was 66-67° C.
  • this compound was prepared with the following differences. 4.3 mmol of 16, 4.3 mmol of silver carbonate and 0.1 mol of hexadecyl iodide were employed. 350 ml of toluene were used as solvent. The temperature was ⁇ 40-100° C. and the reaction time was 10 days (20 ultrasonic warming cycles). The final product was isolated in the same manner as described above. The yield was 1.6 g (46% of theory) of an orange solid having a melting point of 71.5° C.
  • Monomers of the general formula 1, 2 or mixtures thereof were used in amounts of from 1 to 2 mmol.
  • Bis(trialkyltin)thiophenes of the general formula 3 were used in equal molar amounts (or in a 2- to 10-fold excess for the preparation of oligomers).
  • the starting materials were dissolved in anhydrous THF (20-200 ml), introduced into a 2-necked flask which has been dried in an oven or flamed and a gentle stream of nitrogen or argon was passed through the solution for 10 to 15 minutes.
  • the yield was 13% of theory.
  • T is an end group being derived from the monomers used.
  • the reaction time was 24 h.
  • the reaction temperature was 65° C.
  • Purification was carried out by Soxhlet extraction with methanol (24 h) and hexane (24 h). The yield was 39%. A black solid was obtained.
  • the polymer had a weight average molecular weight (M w ) of 29,000 and a polydispersity of 2.1, in each case measured by GPC with the aid of polystyrene as a standard. In the UV spectrum, this polymer showed a ⁇ max of 638 nm (THF).
  • the polymer had an M w of 21,500 and a polydispersity of 2.1, in each case measured by GPC using polystyrene as a standard.
  • the UV spectrum of the polymer exhibited values for ⁇ max at 298 nm, 495 nm and 920 nm (THF).

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US20130102746A1 (en) * 2010-06-25 2013-04-25 Mingjie Zhou Conjugated polymer based on benzodithiophene and thienopyrazine, preparation method thereof and application thereof
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US9378859B2 (en) 2010-08-20 2016-06-28 Rhodia Operations Polymer compositions, polymer films, polymer gels, polymer foams, and electronic devices containing such films, gels and foams
US9552903B2 (en) 2010-08-20 2017-01-24 Rhodia Operations Polymer compositions, polymer films, polymer gels, polymer foams, and electronic devices containing such films, gels and foams
CN110741028A (zh) * 2017-06-01 2020-01-31 住友化学株式会社 高分子化合物的制造方法
CN110741028B (zh) * 2017-06-01 2022-05-03 住友化学株式会社 高分子化合物的制造方法

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JP2000506914A (ja) 2000-06-06

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